Ligand-Centered Hydrogen Evolution with Ni(II) and Pd(II)DMTH.

In this study, we report a pair of electrocatalysts for the hydrogen evolution reaction (HER) based on the noninnocent ligand diacetyl-2-(4-methyl-3-thiosemicarbazone)-3-(2-pyridinehydrazone) (H2DMTH, H2L1). The neutral complexes NiL1 and PdL1 were synthesized and characterized by spectroscopic and electrochemical methods. The complexes contain a non-coordinating, basic hydrazino nitrogen that is protonated during the HER. The pKa of this nitrogen was determined by spectrophotometric titration in acetonitrile to be 12.71 for NiL1 and 13.03 for PdL1. Cyclic voltammograms of both NiL1 and PdL1 in acetonitrile exhibit diffusion-controlled, reversible ligand-centered events at -1.83 and -1.79 V (vs ferrocenium/ferrocene) for NiL1 and PdL1, respectively. A quasi-reversible, ligand-centered event is observed at -2.43 and -2.34 V for NiL1 and PdL1, respectively. The HER activity in acetonitrile was evaluated using a series of neutral and cationic acids for each catalyst. Kinetic isotope effect (KIE) studies suggest that the precatalytic event observed is associated with a proton-coupled electron transfer step. The highest turnover frequency values observed were 6150 s-1 at an overpotential of 0.74 V for NiL1 and 8280 s-1 at an overpotential of 0.44 V for PdL1. Density functional theory (DFT) computations suggest both complexes follow a ligand-centered HER mechanism where the metals remain in the +2 oxidation state.

Aerobic photolysis of methylcobalamin: unraveling the photoreaction mechanism.

The photo-reactivity of cobalamins (Cbls) is influenced by the nature of axial ligands and the cofactor's environment. While the biologically active forms of Cbls with alkyl axial ligands, such as methylcobalamin (MeCbl) and adenosylcobalamin (AdoCbl), are considered to be photolytically active, in contrast, the non-alkyl Cbls are photostable. In addition to these, the photolytic properties of Cbls can also be modulated in the presence of molecular oxygen, i.e., under aerobic conditions. Herein, the photoreaction of the MeCbl in the presence of oxygen has been explored using density functional theory (DFT) and time-dependent DFT (TD-DFT). The first stage of the aerobic photoreaction is the activation of the Co-C bond and the formation of the ligand field (LF) electronic state through the displacement of axial bonds. Once the photoreaction reaches the LF excited state, three processes can occur: namely the formation of OO-CH3 through the reaction of CH3 with molecular oxygen, de-activation of the {Im⋯[CoII(corrin)]⋯CH3}+ sub-system from the LF electronic state by changing the electronic configuration from (dyz)1(dz2)2 to (dyz)2(dz2)1 and the formation of the deactivation complex (DC) complex via the recombination of OO-CH3 species with the de-excited [CoII(corrin)] system. In the proposed mechanism, the deactivation of the [CoII(corrin)] subsystem may coexist with the formation of OO-CH3, followed by immediate relaxation of the subsystems in the ground state. Moreover, the formation of the OO-CH3 species followed by the formation of the {[CoIII(corrin)]-OO-CH3}+ complex stabilizes the system compared to the reactant complex.

Light Mediated Properties of a Thiolato-Derivative of Vitamin B12.

Vitamin B12 derivatives (Cbls = cobalamins) exhibit photolytic properties upon excitation with light. These properties can be modulated by several factors including the nature of the axial ligands. Upon excitation, homolytic cleavage of the organometallic bond to the upper axial ligand takes place in photolabile Cbls. The photosensitive nature of Cbls has made them potential candidates for light-activated drug delivery. The addition of a fluorophore to the nucleotide loop of thiolato Cbls has been shown to shift the region of photohomolysis to within the optical window of tissue (600-900 nm). With this possibility, there is a need to analyze photolytic properties of unique Cbls which contain a Co-S bond. Herein, the photodissociation of one such Cbl, namely, N-acetylcysteinylcobalamin (NACCbl), is analyzed based on density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations. The S0 and S1 potential energy surfaces (PESs), as a function of axial bond lengths, were computed to determine the mechanism of photodissociation. Like other Cbls, the S1 PES contains metal-to-ligand charge transfer (MLCT) and ligand field (LF) regions, but there are some unique differences. Interestingly, the S1 PES of NACCbl contains three distinct minima regions opening several possibilities for the mechanism of radical pair (RP) formation. The mild photoresponsiveness, observed experimentally, can be attributed to the small gap in energy between the S1 and S0 PESs. Compared to other Cbls, the gap shown for NACCbl is neither exactly in line with the alkyl Cbls nor the nonalkyl Cbls.

Utilizing Charge Effects and Minimizing Intramolecular Proton Rearrangement to Improve the Overpotential of a Thiosemicarbazonato Zinc HER Catalyst.

The zinc(II) complex of diacetyl-2-(4-methyl-3-thiosemicarbazone)-3-(2-hydrazonepyridine), ZnL1 (1), was prepared and evaluated as a precatalyst for the hydrogen evolution reaction (HER) under homogeneous conditions in acetonitrile. Complex 1 is protonated on the noncoordinating nitrogen of the hydrazonepyridine moiety to yield the active catalyst Zn(HL1)OAc (2) upon addition of acetic acid. Addition of methyl iodide to 1 yields the corresponding methylated derivative ZnL2I (3). In solution, partial dissociation of the coordinated iodide yields the cationic derivative 3'. Complexes 1-3 were characterized by 1H NMR, FT-IR, and UV-visible spectroscopies. The solid-state structures of 2 and 3 were determined by single crystal X-ray diffraction. HER studies conducted in acetonitrile with acetic acid as the proton source yield a turnover frequency (TOF) of 7700 s-1 for solutions of 1 at an overpotential of 1.27 V and a TOF of 6700 s-1 for solutions of 3 at an overpotential of 0.56 V. For both complexes, the required potential for catalysis, Ecat/2, is larger than the thermodynamic reduction potential, E1/2, indicative of a kinetic barrier attributed to intramolecular proton rearrangement. The effect is larger for solutions of 1 (+440 mV) than for solutions of 3 (+160 mV). Controlled potential coulometry studies were used to determine faradaic efficiencies of 71 and 89% for solutions of 1 and 3, respectively. For both catalysts, extensive cycling of potential under catalytic conditions results in the deposition of a film on the glassy carbon electrode surface that is active as an HER catalyst. Analysis of the film of 3 by X-ray photoelectron spectroscopy indicates the complex remains intact upon deposition. A proposed ligand-centered HER mechanism with 1 as a precatalyst to 2 is supported computationally using density functional theory (DFT). All catalytic intermediates in the mechanism were structurally and energetically characterized with the DFT/B3LYP/6-311g(d,p) in solution phase using a polarizable continuum model (PCM). The thermodynamic feasibility of the mechanism is supported by calculation of equilibrium constants or reduction potentials for each proposed step.

How does the mutation in the cap domain of methylcobalamin-dependent methionine synthase influence the photoactivation of the Co-C bond?

Methionine synthase (MetH) is a methylcobalamin (MeCbl)-dependent mammalian enzyme which plays a critical role in carrying out the transfer of a methyl group from methyl tetrahydrofolate to homocysteine to generate methionine and tetrahydrofolate. This catalytic cycle proceeds via cleavage of a Co-C bond which is formally heterolytic. This cleavage results in a structural change in the MeCbl cofactor bound to an enzyme. Unlike the native catalysis, upon photoexcitation, the Co-C bond in MeCbl-bound MetH generates the Co(ii)/CH3 radical pairs (RPs). Protein residues of the cap domain, particularly phenylalanine708 (F708) and leucine 715 (L715), which surrounds the upper face of the MeCbl cofactor, inhibit the photolysis of MeCbl by caging the CH3 radical and inducing the geminate recombination of the Co(ii)/CH3 RP. A molecular-level understanding of these effects requires a detailed investigation of the low-lying electronic states. Toward this, we have mutated the F708 residue with alanine (A708) and constructed the potential energy surfaces (PESs) for the low-lying S1 electronic state using a combined quantum mechanics/molecular mechanics (QM/MM) approach. The S1 PESs for the wild-type (WT) and mutant enzymes are the result of crossing of two electronic states, namely metal-to-ligand charge transfer (MLCT) and ligand field (LF) states, indicated by a seam. It is shown that the topologies of the S1 PESs are significantly modulated by introducing a mutation at the F708 position. Specifically, for the WT enzyme, the energy barrier of photoreaction and the energy difference between MLCT and LF minima are markedly higher than those of its mutant counterpart. Moreover, mutation influences the photoactivation of the Co-C bond in enzyme-bound MeCbl by decreasing the rate of geminate recombination and altering the rate of radical pair formation. This theoretical insight was also compared with transient absorption spectroscopic (TAS) studies which are in good agreement with the present findings.

Ligand-Assisted Metal-Centered Electrocatalytic Hydrogen Evolution upon Reduction of a Bis(thiosemicarbazonato)Ni(II) Complex.

In this study, we report the electrocatalytic behavior of the neutral, monomeric Ni(II) complex of diacetyl-bis( N-4-methyl-3-thiosemicarbazonato), NiL1, for ligand-assisted metal-centered hydrogen evolution in acetonitrile (ACN) and dimethylformamide (DMF). Using foot-of-the-wave analysis (FOWA), NiL1 displays a maximum turnover frequency (TOF) of 4200 and 1200 s-1 for acetic acid (CH3COOH) in ACN and DMF, whereas for trifluoroacetic acid (CF3COOH) the TOFs are 1300 and 120 s-1 in ACN and DMF, respectively. In ACN, the overpotentials are 0.53 and 0.67 V for CH3COOH and CF3COOH, respectively. In DMF, the overpotential is 0.85 V for CH3COOH. First-order dependence with respect to the catalyst is established. NiL1 displays a minimum Faradaic efficiency of 87% from controlled potential electrolysis. Gas analysis from controlled potential electrolysis in both ACN and DMF using CH3COOH and CF3COOH confirms NiL1 as an electrocatalyst to produce H2. In ACN, TONs of 48 and 24 were obtained for CH3COOH and CF3COOH, respectively in 4 h. In DMF, TONs of 13 and 3 were obtained for CH3COOH and CF3COOH, respectively. The H2 evolution reaction was evaluated using deuterated acid, demonstrating an inverse kinetic isotope, which is consistent with formation of a metal hydride intermediate. A proposed ligand-assisted metal-centered mechanism for HER is supported by computational investigations. All catalytic intermediates in the proposed mechanism were structurally and energetically characterized using density functional theory (DFT), with the B3LYP/6-311g(d,p) and BP86/TZV/P in solution modeled via polarizable continuum model. The final step of catalysis involves the reaction of [HNi(L1·)]- with H+ generating H2. The correctness of proposed mechanism was confirmed by location of corresponding transition state (TS) having single imaginary frequency ( i1786 cm-1).

Photolytic Properties of Antivitamins B12.

Antivitamins B12 represent an important class of vitamin B12 analogues that have gained recent interest in several research areas. In particular, 4-ethylphenylcobalamin (EtPhCbl) and phenylethynylcobalamin (PhEtyCbl) exemplify two such antivitamins B12 which have been characterized structurally and chemically. From a spectroscopic point of view, EtPhCbl is photolabile with a very low quantum yield of photoproducts, while PhEtyCbl is incredibly photostable. Herein, DFT and TD-DFT computations are provided to explore the photolytic properties of these compounds to shed light on the electronic properties that are indicative of these differences. Potential energy surfaces (PESs) were constructed to investigate the mechanisms of photodissociation leading to radical pair (RP) formation and the mechanisms of deactivation to the ground state. The S1 PESs for each antimetabolite contain two energy minima, one being the metal-to-ligand charge transfer (MLCT) and another the ligand-field (LF) state. There are two possible pathways for photodissociation that can be identified for EtPhCbl but only one (path B) is energetically feasible and involves the lengthening of the Co-NIm bond through the MLCT region followed by the lengthening of the Co-C bond through the LF region. For PhEtyCbl, there is not an energetically favorable path for photolysis; rather, internal conversion (IC) is the significantly preferred photophysical event.

Off to the Races: Comparison of Excited State Dynamics in Vitamin B12 Derivatives Hydroxocobalamin and Aquocobalamin.

Ultrafast time-resolved spectroscopy was used to study the photochemistry of hydroxocobalamin (HOCbl) and aquocobalamin (H2OCbl+) in solution. Spectroscopic measurements and TD-DFT simulations provide a consistent picture of the spectroscopy and photochemistry. Excitation of H2OCbl+ results in formation of an excited state followed by rapid internal conversion to the ground state (0.35 ± 0.15 ps) through an S1/S0 seam at a slightly elongated Co-O bond length and a significantly elongated Co-NIm bond length. In contrast, the initial elongation of the axial bonds in HOCbl is followed by contraction to an excited state minimum with bonds slightly shorter than those in the ground state. Internal conversion to the ground state follows on a picosecond time scale (5.3 ± 0.4 ps). For both compounds, photodissociation forming cob(II)alamin and hydroxyl radicals (∼1.5% yield) requires excitation to highly excited states. Dissociation is mediated by competition between internal conversion to the S1 surface and prompt bond cleavage.

Ultrafast X-ray Absorption Near Edge Structure Reveals Ballistic Excited State Structural Dynamics.

Polarized ultrafast time-resolved X-ray absorption near edge structure (XANES) allows characterization of excited state dynamics following excitation. Excitation of vitamin B12, cyanocobalamin (CNCbl), in the αß-band at 550 nm and the γ-band at 365 nm was used to uniquely resolve axial and equatorial contributions to the excited state dynamics. The structural evolution of the excited molecule is best described by a coherent ballistic trajectory on the excited state potential energy surface. Prompt expansion of the Co cavity by ca. 0.03 Å is followed by significant elongation of the axial bonds (>0.25 Å) over the first 190 fs. Subsequent contraction of the Co cavity in both axial and equatorial directions results in the relaxed S1 excited state structure within 500 fs of excitation.

Polarized XANES Monitors Femtosecond Structural Evolution of Photoexcited Vitamin B12.

Ultrafast, polarization-selective time-resolved X-ray absorption near-edge structure (XANES) was used to characterize the photochemistry of vitamin B12, cyanocobalamin (CNCbl), in solution. Cobalamins are important biological cofactors involved in methyl transfer, radical rearrangement, and light-activated gene regulation, while also holding promise as light-activated agents for spatiotemporal controlled delivery of therapeutics. We introduce polarized femtosecond XANES, combined with UV-visible spectroscopy, to reveal sequential structural evolution of CNCbl in the excited electronic state. Femtosecond polarized XANES provides the crucial structural dynamics link between computed potential energy surfaces and optical transient absorption spectroscopy. Polarization selectivity can be used to uniquely identify electronic contributions and structural changes, even in isotropic samples when well-defined electronic transitions are excited. Our XANES measurements reveal that the structural changes upon photoexcitation occur mainly in the axial direction, where elongation of the axial Co-CN bond and Co-NIm bond on a 110 fs time scale is followed by corrin ring relaxation on a 260 fs time scale. These observations expose features of the potential energy surfaces controlling cobalamin reactivity and deactivation.

Translation of Ligand-Centered Hydrogen Evolution Reaction Activity and Mechanism of a Rhenium-Thiolate from Solution to Modified Electrodes: A Combined Experimental and Density Functional Theory Study.

The homogeneous, nonaqueous catalytic activity of the rhenium-thiolate complex ReL3 (L = diphenylphosphinobenzenethiolate) for the hydrogen evolution reaction (HER) has been transferred from nonaqueous homogeneous to aqueous heterogeneous conditions by immobilization on a glassy carbon electrode surface. A series of modified electrodes based on ReL3 and its oxidized precursor [ReL3][PF6] were fabricated by drop-cast methods, yielding catalytically active species with HER overpotentials for a current density of 10 mA/cm2, ranging from 357 to 919 mV. The overpotential correlates with film resistance as measured by electrochemical impedance spectroscopy and film morphology as determined by scanning and transmission electron microscopy. The lowest overpotential was for films based on the ionic [ReL3][PF6] precursor with the inclusion of carbon black. Stability measurements indicate a 2 to 3 h conditioning period in which the overpotential increases, after which no change in activity is observed within 24 h or upon reimmersion in fresh aqueous, acidic solution. Electronic spectroscopy results are consistent with ReL3 as the active species on the electrode surface; however, the presence of an undetected quantity of catalytically active degradation species cannot be excluded. The HER mechanism was evaluated by Tafel slope analysis, which is consistent with a novel Volmer-Heyrovsky-Tafel-like mechanism that parallels the proposed homogeneous HER pathway. Proposed mechanisms involving traditional metal-hydride processes vs ligand-centered reactivity were examined by density functional theory, including identification and characterization of relevant transition states. The ligand-centered path is energetically favored with protonation of cis-sulfur sites culminating in homolytic S-H bond cleavage with H2 evolution via H atom coupling.

Photodissociation of ethylphenylcobalamin antivitamin B12.

Biologically active forms of cobalamins are crucial cofactors in biochemical reactions and these metabolites can be inhibited by their structurally similar analogues known as antivitamins B12. Phenylethynylcobalamin (PhEtyCbl) or 4-ethylphenylcobalamin (EtPhCbl) exemplify recently synthesized and structurally characterized antivitamins B12. Herein, DFT and TD-DFT studies of EtPhCbl are provided to explore its photochemical behavior, which may lead to design of arylcobalamins that can be used as therapeutic agents in light activated drug applications. To understand the photolability of EtPhCbl, a potential energy surface (PES) for the photodissociation of the Co-C bond was constructed. The S1 PES contains two energy minima, one being metal-to-ligand charge transfer (MLCT) and another the ligand-field (LF) state. There are two possible pathways for photodissociation: the first pathway (path A) involves initially lengthening the Co-C bond from the MLCT minimum and then elongation of Co-NIm while the second pathway (path B) involves the lengthening of the Co-NIm bond through the MLCT region followed by the lengthening of the Co-C bond through the LF region. It is shown that photodissociation involving path A is not energetically favorable whereas preferable photodissociation of the Co-C bond involves path B.

Beyond Metal-Hydrides: Non-Transition-Metal and Metal-Free Ligand-Centered Electrocatalytic Hydrogen Evolution and Hydrogen Oxidation.

A new pathway for homogeneous electrocatalytic H2 evolution and H2 oxidation has been developed using a redox active thiosemicarbazone and its zinc complex as seminal metal-free and transition-metal-free examples. Diacetyl-bis(N-4-methyl-3-thiosemicarbazone) and zinc diacetyl-bis(N-4-methyl-3-thiosemicarbazide) display the highest reported TOFs of any homogeneous ligand-centered H2 evolution catalyst, 1320 and 1170 s(-1), respectively, while the zinc complex also displays one of the highest reported TOF values for H2 oxidation, 72 s(-1), of any homogeneous catalyst. Catalysis proceeds via ligand-centered proton-transfer and electron-transfer events while avoiding traditional metal-hydride intermediates. The unique mechanism is consistent with electrochemical results and is further supported by density functional theory. The results identify a new direction for the design of electrocatalysts for H2 evolution and H2 oxidation that are not reliant on metal-hydride intermediates.

Mechanism of Co-C photodissociation in adenosylcobalamin.

A mechanism of Co-C bond photodissociation in the base-on form of adenosylcobalamin (AdoCbl) was investigated by time-dependent density functional theory (TD-DFT). The key mechanistic step involves singlet radical pair (RP) generation from the first electronically excited state (S1). To connect TD-DFT calculations with ultra-fast excited state dynamics, the potential energy surface (PES) of the S1 state was constructed using Co-C and Co-NIm axial coordinates. The S1 PES can be characterized by two minima separated by a seam resulting from the crossing of two surfaces, of metal-to-ligand charge transfer (MLCT) character near the minimum, and a shallow ligand field (LF) surface at elongated axial bond distances. Only one possible pathway for photolysis (path A) was identified based on energetic grounds. This pathway is characterized by the first elongation of the Co-C bond, followed by photolysis from an LF state where the axial base is partially detached. A new perspective on the photolysis of AdoCbl is then gained by connecting TD-DFT results with available experimental observations.

Electronically excited states of cob(ii)alamin: insights from CASSCF/XMCQDPT2 and TD-DFT calculations.

The low-lying excited states of cob(ii)alamin were investigated using time-dependent density functional theory (TD-DFT). The performance of TD-DFT calculations was further evaluated using CASSCF/XMCQDPT2, where both four-coordinate and five-coordinate models of cob(ii)alamin were considered. Dependence of electronic structure on the axial base was then investigated using TD-DFT. Consistent with previous benchmarks, the BP86 functional provides a reliable description of the electronically excited states. It was found that the dyz + π → dz(2) character of the D1 state increases with respect to the axial base distance, corresponding to a lowering in energy of anti-bonding dz(2) orbitals, leading to near a degeneracy between the ground, and D1 states in the base-off form.

The role of spin-orbit coupling in the photolysis of methylcobalamin.

The photolysis of the methylcobalamin cofactor (MeCbl) in its base-off form was investigated by considering the extent of spin-orbit coupling (SOC). Triplet Co-C photodissociation pathways previously invoked at the density functional theory level using Landau-Zener theory were further validated with ab initio calculations that combine SOC based on multi-state second order perturbation theory. It was determined that SOC is feasible between singlet and triplet states at elongated Co-C distances, leading to photodissociation from the state having dominant σ(dz(2)) character, by either direct coupling with the lowest singlet states or by crossing with SOC mixed triplets.

Mercury Methylation by Cobalt Corrinoids: Relativistic Effects Dictate the Reaction Mechanism.

The methylation of Hg(II) (SCH3 )2 by corrinoid-based methyl donors proceeds in a concerted manner through a single transition state by transfer of a methyl radical, in contrast to previously proposed reaction mechanisms. This reaction mechanism is a consequence of relativistic effects that lower the energies of the mercury 6p1/2 and 6p3/2 orbitals, making them energetically accessible for chemical bonding. In the absence of spin-orbit coupling, the predicted reaction mechanism is qualitatively different. This is the first example of relativity being decisive for the nature of an observed enzymatic reaction mechanism.

Mechanism of Co-C bond photolysis in methylcobalamin: influence of axial base.

A mechanism of Co-C bond photolysis in the base-off form of the methylcobalamin cofactor (MeCbl) and the influence of its axial base on Co-C bond photodissociation has been investigated by time-dependent density functional theory (TD-DFT). At low pH, the MeCbl cofactor adopts the base-off form in which the axial nitrogenous ligand is replaced by a water molecule. Ultrafast excited-state dynamics and photolysis studies have revealed that a new channel for rapid nonradiative decay in base-off MeCbl is opened, which competes with bond dissociation. To explain these experimental findings, the corresponding potential energy surface of the S1 state was constructed as a function of Co-C and Co-O bond distances, and the manifold of low-lying triplets was plotted as a function of Co-C bond length. In contrast to the base-on form of MeCbl in which two possible photodissociation pathways were identified on the basis of whether the Co-C bond (path A) or axial Co-N bond (path B) elongates first, only path B is active in base-off MeCbl. Specifically, path A is inactive because the energy barrier associated with direct dissociation of the methyl ligand is higher than the barrier of intersection between two different electronic states: a metal-to-ligand charge transfer state (MLCT), and a ligand field state (LF) along the Co-O coordinate of the S1 PES. Path B initially involves displacement of the water molecule, followed by the formation of an LF-type intermediate, which possesses a very shallow energy minimum with respect to the Co-C coordinate. This LF-type intermediate on path B may result in either S1/S0 internal conversion or singlet radical pair generation. In addition, intersystem crossing (ISC) resulting in generation of a triplet radical pair is also feasible.

Mechanism of the S1 excited state internal conversion in vitamin B12.

To explain the photostability of vitamin B12, internal conversion of the S1 state was investigated using TD-DFT. The active coordinates for radiationless deactivation were determined to be elongated axial bonds, overcoming a 5.0 kcal mol(-1) energy barrier between the relaxed ligand-to-metal charge transfer (S1), and the ground (S0) states.

Mechanism of Co-C bond photolysis in the base-on form of methylcobalamin.

A mechanism of Co-C bond photodissociation in the base-on form of the methylcobalamin cofactor (MeCbl) has been investigated employing time-dependent density functional theory (TD-DFT), in which the key step involves singlet radical pair generation from the first electronically excited state (S1). The corresponding potential energy surface of the S1 state was constructed as a function of Co-C and Co-Naxial bond distances, and two possible photodissociation pathways were identified on the basis of energetic grounds. These pathways are distinguished by whether the Co-C bond (path A) or Co-Naxial bond (path B) elongates first. Although the final intermediate of both pathways is the same (namely a ligand field (LF) state responsible for Co-C dissociation), the reaction coordinates associated with paths A and B are different. The photolysis of MeCbl is wavelength-dependent, and present TD-DFT analysis indicates that excitation in the visible α/ß band (520 nm) can be associated with path A, whereas excitation in the near-UV region (400 nm) is associated with path B. The possibility of intersystem crossing, and internal conversion to the ground state along path B are also discussed. The mechanism proposed in this study reconciles existing experimental data with previous theoretical calculations addressing the possible involvement of a repulsive triplet state.